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(Referência obtida automaticamente do Web of Science, por meio da informação sobre o financiamento pela FAPESP e o número do processo correspondente, incluída na publicação pelos autores.)

Intensity Fluctuations in Single-Molecule Surface-Enhanced Raman Scattering

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Autor(es):
dos Santos, Diego P. [1] ; Temperini, Marcia L. A. [2] ; Brolo, Alexandre G. [3]
Número total de Autores: 3
Afiliação do(s) autor(es):
[1] Univ Estadual Campinas, Inst Quim, Dept Fis Quim, CP 6154, BR-13083970 Campinas, SP - Brazil
[2] Univ Sao Paulo, Inst Quim, Dept Quim Fundamental, CP 26-077, BR-05513970 Sao Paulo, SP - Brazil
[3] Univ Victoria, Dept Chem, POB 3065, Victoria, BC V8W 3V6 - Canada
Número total de Afiliações: 3
Tipo de documento: Artigo de Revisão
Fonte: ACCOUNTS OF CHEMICAL RESEARCH; v. 52, n. 2, p. 456-464, FEB 2019.
Citações Web of Science: 6
Resumo

CONSPECTUS: Around 20 years ago, the first reports of single molecule surface-enhanced Raman scattering (SM-SERS) caused a revolution in nanotechnology. Several researchers were quick to recognize the importance of a technique that can provide molecular vibrational fingerprinting at the SM level. Since then, a large amount of work has been devoted to the development of nanostructures capable of SM-SERS detection. A great effort has also been geared toward elucidating the different mechanisms that contribute to the effect. The understanding of the concept of plasmonic SERS hotspots, the role of chemical effects, and the dynamics of atomic and cluster rearrangements in nanometric domains has significantly advanced, driven by new computational and experimental methods used to study SM-SERS. In particular, SERS intensity fluctuations (SIFs) are now recognized as a hallmark of SM-SERS. Interpretation of SM-SERS data must take into consideration temporal and spatial variations as a natural consequence of the extreme localization inherent to surface plasmon resonances. Further analysis of variations in spectral signature, due to either molecular reorientation or photo (or thermal) processes, pointed to a new area that combines the power of SERS fingerprinting at the SM level to modern concepts of catalysis, such as hot-electrons-driven chemistry. This large body of work on the fundamental characteristics of the SM-SERS effect paved the way to the interpretation of other related phenomena, such as tip-enhanced Raman scattering (TERS). Despite all the fundamental progress, there are still very few examples of real applications of SM-SERS. In recent years, our research group has been studying SIFs, focused on different ways to use SM-SERS. The obvious application of SM-SERS is in analytical chemistry, particularly for quantification at ultralow concentrations (below 1 nM). However, quantification using SM-SERS faces a fundamental sampling problem: the analytes (adsorbed in very small amounts, i.e., low surface coverage) must find rare SERS hotspots (areas with intense electric field localization that yields SERS). This limitation leads to strong temporal and spatial variations in SERS intensities, which translates into very large error bars in an experimental calibration curve. We tackled this problem by introducing the concept of ``digital SERS{''}. This approach provided a roadmap for SERS quantification at ultralow concentrations and a potential pathway for a better understanding of the ``reproducibility problem{''} associated with SERS. In this Account, we discuss not only the analytical applications but also other implementations of SM-SERS demonstrated by our group. These include the use of SM-SERS as a tool to probe colloidal aggregation, to evaluate the efficiency of SERS substrates, and to characterize the energy of localized resonances. SERS involves a series of random processes: hotspots are rare; surfaces/clusters constantly reconstruct; and molecules diffuse, adsorb, and desorb. All these pathways contribute to strong fluctuations in SERS intensities. Our work indicates that a statistical view of the effect can lead to interesting insights and the potential to fulfill the promise of this SM technique for real-world applications. (AU)

Processo FAPESP: 18/15987-9 - Fronteiras e desafios da espectroscopia Raman intensificada pela superfície (SERS)
Beneficiário:Marcia Laudelina Arruda Temperini
Linha de fomento: Auxílio à Pesquisa - Pesquisador Visitante - Internacional
Processo FAPESP: 16/21070-5 - Espectroscopia vibracional com resolução espacial
Beneficiário:Mauro Carlos Costa Ribeiro
Linha de fomento: Auxílio à Pesquisa - Temático